Site-Selective Radical Trifluoromethylaminoxylation of Olefins for the Modular Synthesis of Diverse β-Trifluoromethyl Trisubstituted Hydroxylamines and Beyond.

Org Lett

Key Laboratory for Green Organic Synthesis and Application of Hunan Province, Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan, Hunan 411105, P. R. China.

Published: April 2023

A highly site-selective trifluoromethylaminoxylation of activated and unactivated olefins was reported under metal-free conditions. The method provides direct access to diverse β-trifluoromethyl trisubstituted hydroxylamines, tertiary alcohols, isoxazolines, isoxazolidines, and amino alcohols. The SET process between hydroxylamine and the hypervalent iodine-CF reagent is proposed to produce two free radicals for the regio- and diastereoselective addition to alkenes. The synthetic potential of the protocol was established via the late-stage functionalization of the products and a series of postreaction modifications.

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http://dx.doi.org/10.1021/acs.orglett.3c00951DOI Listing

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